I n d . Eng. Chem. Res 1988, 27, 2372-2377
2372
x = continuously variable fiber diameter
p = polymer
Dimensionless G r o u p s ~1 = (QgPg)/(dopg) = Re, = gas Reynolds number n2 = (Q,p,)/(dip,) = Re, = polymer Reynolds number n3 = D/di, die head geometry n4 = d,/di, die head geometry n5 = h/di, die head geometry n6 = d/di = fiber attenuation n7 = p,/p, = viscosity ratio n8 = p p / p = density ratio rg = C = heat capacity ratio n10 = +,Ifg, temperature ratio
Literature Cited
/E
T ITa, temperature ratio = Weber number n13 = ( p , C J / k , - Pr, = polymer Prandtl number 814 = ( p g C g ) / k g= Pr, = gas Prandtl number “15 = c/di nll =
r12= ( 4 , Z p
Greek L e t t e r s p = mean of a normal distribution pup= viscosity of gas, kg m-l s-l s-l pup= viscosity of polymer, kg pg = density of gas, kg m-3
pp =
density of polymer, kg m-3
a = surface energy of polymer, kg s - ~ a2 =
variance of a normal distribution
Subscripts
a = air f = final g = gas i = inner diameter, or a part of an overall size distribution o = out,er diameter, or value at the origin of the threadline
Bringman, D. J.; Buntin, R. R. Development and Commercialization of the Melt-Blowing Process for the Manufacture of Fine Fibrous Webs; Presented a t the Society of Plastics Industry 32nd Annual Technical Conference, San Francisco, CA; Society of Plastics Industry: New York, 1974. Buckingham, E. “On Physically Similar Systems; Illustrations of the Use of Dimensional Equations”. Phys. Reu. 1914, 2, 345. Buntin, R. R.; Keller, J. P.; Harding, J. W. “Non-woven Mats by Melt Blowing”. US Patent 3849241, Nov 19, 1974. Mansfield, R. G. “Microdenier Non-Wovens: Looking for Markets”. Text. World J . 1979, Feb, 83-84. McCulloch, W. J.; Van Brederode, R. A. Technical Deuelopments in the Melt-Blowing Process and I t s Applications in Absorbent Products; Presented a t Insight 81, the Absorbent Products Conference, San Antonio, TX; Miller Freeman: San Francisco, CA, 1981. Narasimhan, K. M.; Shambaugh, R. L. The Melt Blowing of Polyolefins; Presented a t the 59th Annual Meeting of the Society of Rheology, Atlanta, GA; Society of Rheology: New York, 1987. Narasimhan, K. M.; Shambaugh, R. L. “Melt Blowing: General Equation Development and Experimental Verification of a Simplified Model”, submitted for publication in AIChE J . 1988. Schwarz, E. C. A. “Apparatus and Process for Melt Blowing a Fiberforming Thermoplastic Polymer and Product Produced Thereby”. US Patent 4380570, April 19, 1983. Wente, V. A. “Manufacture of Superfine Organic Fibers”. Report PB111437, NRL-4364, April 15, 1954; US Department of Commerce, Office of Technical Services, Washington, DC. Wente, V. A. “Superfine Thermoplastic Fibers”. Ind. Eng. Chem. 1956, 48, 1342. Received for review March 31, 1988 Accepted August 9, 1988
Decomposition and Utilization of Ozone in Water Treatment Reactor with Ultraviolet Radiation Shigeharu Morooka,* Katsuki Kusakabe, Jun-ichiro Hayashi, and Kazuaki Isomurat Department of Applied Chemistry, Kyushu University, Fukuoka 812, J a p a n
Kiyoshi Ikemizu Department of Industrial Chemistry, Toa University, Fukuoka 815, J a p a n
T h e decomposition rate of ozone in the gas phase with ultraviolet irradiation was determined in a thin, rectangular channel reactor where the distributions of ozone concentration and UV irradiation were minimized. The experiment was carried out under conditions which were encountered in normal water treatment units. T h e overall quantum yield of ozone decomposition was correlated by experimental equations. Estimated values of the overall quantum yield based on elementary reactions and kinetic data in the literature were much smaller than the experimental data. The utilization efficiency of ozone in the ozone/UV process for water treatment was simulated with a simple model reactor. Excessive UV radiation is likely to destroy gaseous ozone before i t is transferred into the liquid phase. T h e optimum value of UV irradiance depends on the apparatus and operation conditions. Ozone is one of the most powerful oxidizing reagents and has the advantage that oxidized products are usually less toxic than those that are chlorinated when used in the treatment of water supplies. However, refractory compounds such as saturated alcohols and carboxylic acids are built up in the system after a certain extent of ozonation. These compounds can be oxidized by HO radicals which
* Author to whom correspondence should addressed. ‘Present address: Laboratory for Waste Water Treatment, Kyushu University, Fukuoka 812, Japan.
are generated when the alkalinity of solution is raised, but this method is not preferable in the case of potable water treatment because it needs the addition of foreign chemic&. Therefore, the simultaneous application of ozone and ultraviolet radiation becomes promising, especially to remove trihalomethane precursors (Glaze et al., 1982; Prengle et al., 1975) Ikemizu et al. (1987b) studied the ozonation rate of organic refractory compounds in the presence of UV radiation. They directly measured the dissolved ozone concentration and the UV irradiation in a thin rectangular reactor. 1988 American Chemical Society
Ind. Eng. Chem. Res., Vol. 27, No. 12, 1988 2373 Air suction pump
I
I
I
I
1
I 1,ll
I
A
7
E
E L =T
-Y
/
/
/
/
Actinometer cell
/
0.1 0.1
0.2
Figure 1. Dimensions of photolytic reactor.
A preliminary simulation of ozone utilization in a model reactor implies that unnecessarily intensive UV radiation may destroy ozone in the gas phase before it is transferred into the liquid phase (Ikemizu et al., 1987a). Many works have been published on the photochemistry of gaseous ozone, but most of them are associated with phenomena in the upper atmosphere where the pressure is lower than that encountered in the usual water treatment units (Jones et al., 1970). No practical rate equations for the photolytic decomposition of ozone in the gas phase are published to date. In this study, the decomposition rate of ozone in mixtures of ozone, oxygen, and other common gases is investigated in the presence of ultraviolet radiation. Furthermore, ozone utilization in a water treatment unit is discussed considering the decomposition rate of ozone in the gas and aqueous phases.
Experimental Section Figure 1shows details of the reactor which is sectioned by the vertical plane perpendicular to the gas flow. The reactor was 10 mm wide, 4 mm thick and 190 mm long and was sandwiched with transparent quartz plates 3 mm thick. A low-pressure mercury lamp (20 W, 30 cm long) was used in the experiment, emitting principally at 253.7 nm. The photolytic generation of ozone from oxygen in the reactor was not observed with this wavelength. The UV irradiance (intensity) was determined by potassium ferrioxalate actinometry. The concentration of produced Fez+was measured by spectrophotometry at 510 nm after coloration with 1,lO-phenanthroline. The experiment was carried out at 283-303 K, and the mean UV irradiance was 2-40 W-m-2. The mean ozone concentration was 0.1-2.0 m ~ l . m -and ~ was determined by iodometry. The conversion of ozone was kept within 0.3. The concentration of oxygen was changed by introducing nitrogen or argon continuously into the reactor. Argon was used as an inert diluent (Norrish and Wayne, 1965a). Deionized and distilled water was used in the experiment. All chemicals were reagent grade and were used without further purification. When the conversion of ozone is small, the logarithmic mean of the inlet and outlet concentration of ozone represents the ozone concentration in the reactor. Then the UV irradiance at the upper plane of the lower quartz plate (the lower surface of the reactor), 11,is related to that at the lower plane of the upper quartz plate (the upper surface of the reactor), Io, as follows: 1, = 1110%1C03 (1) where CZG = 295 mol-'.m2 for 253.7 nm (Griggs, 1968) and
/
I
eo3
lb'l
0.5
I
1
I I
I
2
1
[ m o ~ . m -J ~
Figure 2. Effect of gas compositionon overall quantum yield in gas phase at T = 303 K the broken lines are calculated from eq 9; the solid lines indicate the experimental results; gaseous ozone concen- ~ 03-02-air system, (0)20 m ~ l - m for -~ tration, (v) 7.8 m ~ l - m for 39 m ~ l . m for - ~ Os-02 system. 03-02-air system, (0) m VI
I
I
I
I
I
I
20
Coz
[ mol. m-3
I
1
I
1
40
I
Figure 3. Effect of oxygen concentrationon overall quantum yield in gas phase at T = 303 K: the ordinate is corrected with ozone concentration; ( 0 ) 03-02-Ar system, (A) 03-02-Nzsystem.
1 = 4 mm. The UV irradiance averaged along the reactor depth is
I
= (Io - Il)/ln
(b/lJ
(2)
Using eq 1 and 2 gives
I
= 11(104~1c03 - 1)/(2.303aGlCo3)
(3)
The photolytic decomposition rate of ozone in the gas phase was proportional to the amount of absorbed light: -dCo3/dt = &(IO - Ii)/(lhvNA) = 2.303&aJCo,/(hvNA)
(4)
Thus, the overall quantum yield was calculated from
I P ~= (-dCo3/dt)hvNA/(2.303aJCo,)
(5)
Experimental Results and Discussion Figure 2 shows the effect of the oxygen concentration on the quantum yield for 03-Oz and 03-02-Ar systems. The quantum yield was proportional to C0305 in the present experiment. Figure 3 indicates that the quantum yield decreases with an increase in the oxygen concentration. The ordinate is corrected by the ozone concentration. The quantum yield for the 03-02-N2 system is smaller than that for the 03-Oz-Ar system. This means that nitrogen as well as oxygen is involved in the termination step (Glinski and Birks, 1985). An Arrhenius plot of the overall quantum yield is shown in Figure 4. To emphasize the effect of diluent gases for the 03-02-Ar and 03-02-Nz systems, data at lower oxygen concentrations (7.5-7.7 m ~ l . m - ~are ) plotted here. The
2374
Ind. Eng. Chem. Res., Vol. 27, No. 12, 1988 I
33
I
I
I
36 103y
35 K-i
1
Figure 4. Arrhenius plot of overall quantum yield in gas phase corrected with ozone concentration: (0)03-02-Ar system, (A) 0,-02-Nz system. (0) 03-O2 system.
41
0.2 0.2 (
I
0.5
1
)caic
c-1
2
Figure 6. Comparison between experimental results and calculated values from eq 6 and 7 .
I
-8-”
i;
05
I
1
I
10
15
20
C H ~ O[
mol “ 3 1
F i g u r e 5. Effect of water vapor concentration of overall quantum yield in gas phase corrected with ozone concentration at T = 303 K: the ordinate is corrected with ozone concentration; (V)CO,= 7.8 m ~ l e m -for ~ Os-air-HzO system, (0) CO, = 39 m o l ~ m for - ~ 03-02-H20 system.
activation energy was 23 kJ.mol-’, and no effect of the gas composition was observed. Figure 5 illustrates the effect of water vapor on the quantum yield. When the oxygen concentration is as low as it is in ambient air, the quantum yield increases with increasing water vapor concentration. This corresponds to the results of Norrish and Wayne (1965b) and Ogren et al. (1982). For the 03-O2 systems with abundant oxygen, however, the quantum yield is independent of the water concentration. From the above, we correlate the overall quantum yield for the ozone decomposition in the gas phase with irradiation of 253.7 nm as follows: for oxygen concentrations higher than ambient air: @G
0 Jones 0.1 -
A 0
0.05
and Wayne (19701, Co3=1.6mol.m3 Norrish and Wayne (1965), Co,=O.l mol ni3 This work
c 0.02 1
I 2
I
I
I I
///I 10
5
P
\
\ \
\ \ \
I
20 IkPa3
I
l l ! ! l ?
50
100
Figure 7. Effect of total pressure on overall quantum yield in gas phase for Co3 = 1.6 and 0.1 Table I. Decomposition Reactions of Ozone i n Gaseous Phase
= 7.9 x IO4 exp(-23 kJ.mol-’/RT) x
C03O5(CO2+ CNz(f7)-0,7(6)
for oxygen concentration of ambient air: @G
= (eq 6)(1 + O.~CH,O)
(7)
where the unit of concentration is m ~ l . m -and ~ Figure 6 shows that the experimental data are well correlated by eq 6 and 7 . Figure 7 is the comparison between the experimental data in the literature (Jones and Wayne, 1970; Norrish and Wayne, 1965a) and the calculation from eq 6 and 7 . The data of Norrish and Wayne (1965a) at Co, = 0.1 m o l ~ m - ~ are in good agreement with the present correlations. Elementary reactions in the photolytic decomposition of gaseous ozone at low pressures were reviewed by Ogren et al. (19821, Podolske and Johnston (19831, and Glinski and Birks (1985). Table I shows the major reactions for the 03-02-H20 system. The propagation reactions among excited species and the termination reactions against the reactor wall and with nitrogen are neglected compared with
-- -
O@P)+ O,’+ H 2 0 O3 + H 2 0 Oz(’A,) + H20 0 2 + H20 0z(IZg) + HzO 0 2 + HzO HO + O3 H 0 2 + O2 HOz + 0 3 HO + 202
-
-+
reactions between excited species and abundant oxygen. The splitting of water into Hz and O2 by O(lD) is 2 orders of magnitude slower than reaction G14 (Podolske and Johnston, 1983) and is also neglected in Table I.
Ind. Eng. Chem. Res., Vol. 27, No. 12, 1988 2375
i G i i (bubble)
1
x=o '$3
I
UG
Figure 8. Model of ozone/UV reactor.
When steady state among concentrations of excited species in Table I is assumed, the decomposition rate of ozone for the 03-O2 system is expressed by
The last assumption is valid only when organic compounds are refractive to ozone and the concentration of radical scavengers is not high. This situation may be realized in the treatment of drinking water. The decomposition of ozone in the liquid film causes no appreciable increase in the overall-mass-transfer capacity coefficient, K G u , in the range of Z 5 100 W.m-2. From the above, the ozone concentrations in the gas and liquid phases are described by -UG dCo3/dx - ~ . ~ O ~ € G ' # ' G ~ J C O , / (-~ V N A ) KGa(C0, - [03IH) = 0 (10) K G ~&(L T c ~ 3 / dx L ~- [031H) 2.303(1 - CG)'#'LULI[O~]/(~~NA) = 0 (11) The first term of eq 10 stands for the transportation of gaseous ozone in ascending bubbles, the second term the consumption rate of ozone in the gas phase, and the third term the mass-transfer rate of ozone into the liquid phase. The first term of eq 11 is the mass-transfer rate of ozone into the liquid phase, and the second one is the decomposition rate of ozone in the liquid phase. Since the ozone concentration in the liquid phase is constant by the assumption ii, the ozone concentration in the gas phase must be integrated in eq 11. The gaseous ozone concentrations in eq 10 and 11 are expressed on the basis of the unit volume of the reactor. Equations 10 and 11 are solved numerically with the following boundary conditions:
x=0
where K1 = k3 + k4 + k5 and K2 = k6 + k7. k l - k13 corresponds to reactions Gl-Gl3 in Table I. The overall quantum yield is calculated from
co, = co;
(12)
Quantum Yield for Ozone Decomposition. In order to calculate eq 10-12, one must know the quantum yield for ozone decomposition both in the gas and liquid phases. The quantum yield for the gaseous ozone is given by eq 6 and 7. Meanwhile, that for the dissolved ozone can be derived from the experimental results of Morooka et al. (1978) and Ikemizu et al. (1987a). The self-decomposition rate of ozone in the aqueous phase without UV irradiation is expressed by the following equations (Morooka et al., 1978): -d[O,]/dt
+
= k,[OH-]0'28[03]1.5 kb[OH-][03] (13)
where and is plotted in Figures 2 and 7, where we adopted the kinetic data of Ogren et al. (1982) and Glinski and Birks (1985). The intrinsic quantum yield for reactions G1 and G2 are 0.85 and 0.15, respectively (Ogren et al., 1982). Our experimental data are quite larger than the calculation from eq 9, although the reaction schemes can qualitatively explain the experimental results. This indicates that the data in the literature are acceptable only at oxygen pressure lower than 10 kPa. Utilization of Ozone Reactor Modeling. The decomposition of ozone in the gas phase increases with an increase in the UV irradiance, and the gaseous ozone is destroyed before it is absorbed into the solution. Thus, the efficiency of ozonation in a reactor for water treatment is dependent on the loss in the gas phase as well as in the liquid phase. Figure 8 is a schematic expression of a model reactor. The simulation is based on the following assumptions: (i) The gas phase is in plug flow. (ii) The liquid phase is in backmix flow. (iii) The UV irradiance and the OH- concentration are constant anywhere in the reactor. (iv) Dissolved organic compounds do not influence the decomposition rate of ozone.
k , = 2.1
X
lo1' exp(-74.9 kJ-mol-'/RT)
kb = 1.8 X 1015 exp(46.2 kJ-mol-l/RT)
(14) (15)
The unit of concentration is m ~ l - m - ~The . first term in the right-hand side of eq 13 is the decomposition rate of ozone in acidic solutions, and the second one is that in alkaline solutions. Equation 13 was derived on the basis of the data of Morooka et al. (1978) as well as Czapski et al. (19861, Hewes and Davison (19711, Rothmund and Burgstaller (1913), and Stumm (1954). Teramoto et al. (1981) confirmed that eq 13 agrees well with their experiment although the existing data were not reproducible in the acidic region (Sotelo et al., 1987). The first-order reaction with respect to the pH value and the ozone concentration in the alkaline region was experimentally supported by Rizzuti et al. (1976), Czapski et al. (1986), S t u " (1954), and Teramoto et al. (1981). In the presence of the UV radiation, however, the decomposition rate of dissolved ozone is much accelerated. The initiation step of the ozone decomposition in the presence of UV radiation is (Peyton and Glaze, 1987) O3 + H20 + hv O2 + H z 0 2 (16)
-
Although the reaction between Hz02and ozone is slow,
2376 Ind. Eng. Chem. Res., Vol. 27, No. 12, 1988 1.0,
I
-
I
I
4
, , I , /
7
I
10
I
,
, l , l , ,
c;3= 0.1mol,m3
4-02-H20
tw
-
1 00
I
m-2~
Figure 9. Effect of UV irradiance on RG and RL as a function of inlet ozone concentration: pH 7, T = 293 K, LT = 5 m, c~ = 0.031, H = 3.23, KGQ= 5.8 X s-l, U , = 0.01 m 8.
H02- produced by the dissociation of H202quickly reacts with ozone (Staehelin and Hoigne, 1982): H 2 0 2e H02- + H+ (17) Then HOz- is involved in the radical chain reactions. The photolytic decomposition rate of H202is more than 2 orders of magnitude slower than that of reaction 17 (Podolske and Johnston, 1983) and is not an important step of the chain reactions. Ikemizu et al. (1987a) presented the following equation considering the decomposition initiated by both OH- and UV irradiation: -dCo,/dt = k,[OH-]0~2s[03]1.5 + IZb[OH-][03] + 2.8 exp(-16 kJ-mol-'/RT) [ OH-]0.07[03]f(18) where the unit of concentration is m ~ l . m - ~If . the UV irradiance is larger than several W.m-2 around neutral pH values, the decomposition by the first and second terms in the right-hand side of eq 17 becomes negligible. Then the overall quantum yield in the liquid phase is derived in the same manner as in the gas phase: @L = (-d[O,]/dt)hvN~/(2.303aJ[o,]) = 2.8hvNA exp(-16 kJ.mol-l/ RT)[OH-]0.07/(2.303~L)(19) This equation is valid under the following conditions: pH 2-9, T = 279-303 K, I = 2-40 W.m-2, [O,]= 0.03-0.4 m o l ~ m - ~The . experimental data of $L exist in the range 0.7-2 a t 303 K. The reaction scheme presented by Peyton and Glaze (1987) suggests that three ozone molecules are consumed when one ozone molecule reacts with a photon. Then the quantum yield for the decomposition of ozone in the solution without radical scavengers is given by
4L
2 3
(20)
This value of @L is much larger than the experimental one correlated by eq 19, which implies that the dissociation of H202 is slow compared with other reactions. Numerical Calculation. Figures 9 and 10 show typical results of the calculation. The fraction of decomposed ozone in the gas and aqueous phase is defined by RG = (amount of ozone decomposed in gas phase)/ (amount of ozone introduced into the reactor) (21)
RL = (amount of ozone decomposed in liquid phase)/(timount of ozone introduced into the reactor) (22)
Equation 21 indicates the meaningful fraction of reacted ozone in the water treatment unit. The optimum value
c w ni21
Figure 10. Effect of UV irradiance on RG and RL for 03-02-H20 system as a function of superficial gas velocity: pH 7, T = 293 K, LT = 5 m, cG = 0.031, H = 3.23, KGQ = 5.8 X s?, CO; = 2
m~l.m-~.
of UV irradiation normally exists in the range 10-100 W.m-2 and depends on reactor dimensions and operational conditions. The calculation in the previous paper (Ikemizu et al., 1987a) was not sufficient because the quantum yield in the gas phase, @ G , was assumed to be unity because of the lack of information a t that time. The present result apparently indicates that the reactor system must be optimized considering the reaction of ozone in the gas phase as well as the aqueous phase. Conclusions The decomposition rate of ozone in the gas phase was measured a t conditions encountered in water treatment units in the presence of UV radiation. Experimental data of the overall quantum yields for the ozone decomposition were well correlated with eq 6 when the oxygen concentration was higher than ambient air. At Co 20 kPa, the overall quantum yields were affected by the water vapor concentration as indicated by eq 7. The overall quantum yield which was calculated from elementary reactions in Table I was much smaller than the experimental value a t ambient pressure. The kinetic data in the literature were acceptable only in the range P 10 kPa. The utilization efficiency of ozone in a model reactor for water treatment in the presence of UV radiation was estimated using the overall quantum yields in the gas and aqueous phases. An optimum value of UV irradiation appeared in the range 10-100 W.m-2. '-
Acknowledgment This work was supported by Grant-in-Aid for Scientific Research on Priority Areas (Grant 62602530), the Ministry of Education, Science and Culture, Japan. The authors are grateful to Prof. Hiroshi Taniguchi, Department of Applied Chemistry, Kyushu University, for the useful discussion. Nomenclature uG = absorption coefficient of light (base 10) in gas phase, mol-'.m2 QL = absorption coefficient of light (base 10) in liquid phase, mol-'.m2 CHao= concentration of water in gas phase, m ~ l . m - ~ Cx2 = concentration of nitrogen in gas phase, m ~ l n m - ~ Co, = concentration of oxygen in gas phase, m ~ l q m - ~ Co, = concentration of ozone in gas phase, m ~ l e m - ~ Co,O = concentration of ozone in gas phase at x = 0, m ~ l e m - ~ H = Henry's constant (molar concentration in gas phase)/ (molar concentration in liquid phase) h = Plank's constant, J.s i = mean IJV irradiance in reactor, W.m-'
I n d . Eng. Chem. Res. 1988,27, 2377-2384
I,, I , = UV irradiance defined i n Figure 1, W.m-2 K G u = capacity coefficient for mass transfer between bubble a n d liquid phase, s-’ k , = reaction rate coefficient defined in eq 14, mo14~78.m2.34.s-’ k b = reaction r a t e coefficient defined in e q 15 mol-’-m3-s-’ k i = reaction r a t e coefficient for ith reaction i n T a b l e I LT = height of water t r e a t m e n t unit, m 1 = thickness of rectangular reactor i n Figure 1, m N A = Avogadro’s n u m b e r , mol-l [0,] = concentration of ozone i n liquid phase, m o l d [OH-] = concentration of OH- i n liquid phase, m ~ l - m - ~ P = t o t a l pressure, Pa R = gas constant, J.mo1-l.K-l RG = fraction of ozone reacted in gas p h a s e RL = fraction of ozone reacted i n liquid phase T = temperature, K t = time, s UG = superficial gas velocity, ms-’ x = axial coordinate from b o t t o m of reactor, m
Greek Symbols = gas h o l d u p i n water t r e a t m e n t reactor Y = frequency of light 4G = overall q u a n t u m yield for ozone decomposition i n gas CG
phase
&, = overall q u a n t u m yield for ozone decomposition in liquid phase
Literature Cited Czapski, G.; Samuni, A.; Yelin, R. “The Disappearance of Ozone in Alkaline Solution”. Isr. J . Chem. 1986,6,969-971. Glaze, W. H.; Peyton, G. R.; Lin, S.; Huang, R. Y.; Burleson, J. L. “Destruction of Pollutants in Water with Ozone in Combination with Ultraviolet Radiation. 2. Natural Trihalomethane Precursors”. Environ. Sci. Technol. 1982,16,454-458. Glinski, R. J.; Birks, J. W. “Yields of Molecular Hydrogen in the Elementary Reactions HOz + H 0 2 and O(lD,) + HzO“. J. Phys. Chem. 1985,89,3449-3453. Griggs, M.; “Absorption Coefficients of Ozone in the Ultraviolet and Visible Regions”. J. Chem. Phys. 1968,49,857-859. Hewes, C. G.; Davison, R. R. “Kinetics of Ozone Decomposition and Reaction with Organics in Water”. AIChE J . 1971,17,141-147. Ikemizu, K.; Morooka, S.; Kato, Y. “Decomposition of Ozone in Water with Ultraviolet Radiation”. J . Chem. Eng. Jpn. 1987a,20, 77-81. Ikemizu, K.; Orita, M.; Sagiike, M.; Morooka, S.; Kato, Y. “Ozonation of Organic Refractory Compounds with UV Radiation”. J. Chem. Eng. Jpn. 1987b,20,369-374. Jones, I. T. N.; Wayne, R. D. “The Photolysis of Ozone by Ultraviolet
2377
Radiation IV. Effect of Photolysis Wavelength on Primary Step”. Proc. R. SOC.London, Ser. A 1970,A.319,273-287. Jones, I. T. N.; Kaczmar, U. B.; Wayne, R. P. “The Photolysis of Ozone by Ultraviolet Radiation 111. The Photolysis of Dry Ozone/Oxygen Mixtures a t Low Pressures in a Flow System”. Proc. R. SOC.London, Ser. A 1970,A.316, 431-439. Morooka, S.; Ikemizu K.; Kato, Y. “The Decomposition of Ozone in Aqueous Solution”. Kagaku Kogaku Ronbunshu 1978,4,377-380; translated in Int. Chem. Eng. 1979,19,650-654. Norrish, R. G. W.; Wayne, R. P. “The Photolysis of Ozone by U1traviolet Radiation I. The photolysis of Pure, Dry Ozone”. Proc. R. SOC.London, Ser. A 1965a,A.288, 200-211. Norrish, R. G. W.; Wayne, R. P. “The Photolysis of Ozone by U1traviolet Radiation 11. The Photolysis of Ozone Mixed with Certain Hydrogen-containing Substances”. Proc. R. SOC.London, Ser. A 196513,A.288,361-370. Ogren, P. J.; Sworski, T. J.; Hachanadel, C. J.; Cassel, J. M. “Flash Photolysis of O3 in O2and 0, + Hz Mixtures. Kinetics of 02(’22) + O3 and O(’D) + H, Reactions”. J . Phys. Chem. 1982,86, 238-242. Peyton, G. P.; Glaze, W. H. “Mechanism of Photolytic Ozonation”. In Photochemistry of Environmental Aquatic Systems; Zika, R. G., Cooper, W. J. Eds.; ACS Symposium Series 327; American Chemical Society: Washington, DC, 1987; pp 76-88. Podolske, J. R.; Johnston, H. S. “Rate of Reaction Energy-Transfer Reaction between O p ( l A g )and HOO”. J. Phys. Chem. 1983,87, 628-634. Prengle, H. W., Jr.; Mauk, C. E.; Legan, R. W.; Hewes, C. G., 111. “Ozone/UV Process Effective Wastewater Treatment”. Hydrocarbon Process. 1975,Oct, 82-87. Rizzuti, L.; Augugliaro, V.; Marrucci, G. “Ozone Absorption in Alkaline Solutions”. Chem. Eng. Sci. 1976,31,877-880. Rothmund, V.; Burgstaller, A. “Uber die Geschwindigkeit der Zersetzung des Ozons in Wasserrger Losung”. Monatsh. Chem. 1913, 34,665-693. Sotelo, J. L.;Beltran, F. L.; Benites, F. J.; Beltran-Heredia, J. “Ozone Decomposition in Water: Kinetic Study”. Ind. Eng. Chem. Res. 1987,26,39-43. Staehelin, J.; Hoigne, J. “Decomposition of Ozone in Water: Rate of Initiation by Hydrogen Ions and Hydrogen Peroxide”. Enuiron. Sei. Technol. 1982,16,676-682. Stumm, W. “Der Zerfall von Ozon in Wassriger Losung”. Helu. Chem. Acta 1954,37,773-778. Teramoto, M.; Imamura, S.; Yatagai, N.; Hishikawa, Y.; Teranishi, H. “Kinetics of the Self-Decomposition of Ozone and the Ozonation of Cyanide Ion and Dyes in Aqueous Solutions”. J . Chem. Eng. J p n . 1981,14,383-388.
Received for review December 21, 1987 Revised manuscript received J u n e 20, 1988 Accepted August 20, 1988
Generalized Viscosity Behavior of Fluids over the Complete Gaseous and Liquid States Huen Lee* Department of Chemical Engineering, Korea Institute of Technology, 400, Kusong-dong, Seo-gu, Taejon-shi, Chung-chong nam-do, Korea
George Thodos Department of Chemical Engineering, Northwestern University, Euanston, Illinois 60201
A generalized correlation of viscosity of both nonpolar and polar fluids over the entire temperature and pressure ranges has been developed. In addition to the triple-point properties, a volume expansion factor, defined as the ratio of liquid molar volume to solid molar volume at the triple point, was employed. Comparison between experimental and predicted values for 101 substances shows an average absolute deviation of 4.03% (2515 p o i n t s ) . The present state of our k n o w l e d g e d e a l i n g w i t h the generalized prediction of the transport properties continues to be limited to t h e dilute and m o d e r a t e l y dense g a s e o u s states. A t t e m p t s to extend this g- e n e r a l i z e d a -p p- r o a c h to
* Author t o whom
correspondence should be addressed.
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gases at high pressures and the liquid state associated w i t h t e m p e r a t u r e s below the normal boiling p o i n t and app r o a c h i n g the triple-point region of substances h a v e not y e t been p r o p e r l y resolved to p e r m i t the formulation of a unified approach for viscosity; thermal conductivity, ar d self-diffusivity. Because of the complexity associated w i t h 0 1988 American Chemical Society
